Textile finishing



Eatentcd June 3Q, 1942 I v'v'yly M. Billing, Wilmington, Del., minor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware l'\'c Drawing. Application June 23, 1939, Serial No. 280,807

14 Claims. (Cl. 117-143) This invention relates to an improved textile fabric and to methods of production thereof. More particularly, it relates to a textile fabric characterized by an improved flexible finish and to methods of producing the same.

Heretofore textile fabrics have been sized with starches. gums, softeners, etc., to fill up and add body to the fabric. When starch is used in the heavy sizing of duck and in back filling finishes for lining materials it dusts out of the fabrics to a considerable extent on shaking of the fabric. Starches also produce cloudy surface coatings whenapplied in heavy concentrations. In back filling of colored fabrics with starch, it is necessary to include a dye in the mix to compcnsate for the reduced strength of shade caused by the cloudiness of the starch finish. Also, heavily starched fabrics possess a distinct boardiness which impairs flexibility.

It is the object of this invention to provide an improved method of finishing textile fabrics and to produce thereby finished textile fabrics having an improved flexible finish.

It is another object of this invention to provide an improved method of finishing textile fabrics with starches, softeners and other materials commonly used in such operations so as to provide a textile fabric having improved properties over those heretofore obtainable, particularly improved body and fullness. The finish obtained has the advantages of starch finishes generally without the usual disadvantages. Other features of the invention are evidenced in the finishing of various types of textile fabrics with the various formulations of finishes in accordance with this invention.

The invention is applicable to either pure or back-filled finishes. Thus in the finishing of spun rayon a very satisfactory handle and body are developed. In the back filling of lining cloth with the usual starches, talc and softeners, my improved method and finishing composition provide a finished fabric which is free from dusting out" of starch and talc and which has im proved flexibility and resistance to breaking of the fabric. In the finishing of colored fabrics with starch, my improved finishing composition and method provide a finish which possesses increased color brightness over that obtainable with the usual starch treatment, In addition, the

starch particles are more firmly adherent to the fabric. A similar increased color brightness may be obtained by dyeing the fabric after it has been finished according to this invention. In the finishing of hosiery, my improved method binds the cross threads at their point of contact and thereby produces runproof properties.

The above highly desirable features of my invention are realized by treating a textile fabric with a finishing composition comprising as an essential constituent a polyhydric alcohol ester of a rosin, having a melting point (Hercules drop method) within the range of about 35 C. to about 70' C. In accordance with this invention, I have found that such an ester of rosin possesses very unique properties highly advantageous in textile finishing compositions. Being of the thermoplastic type and having resinous properties, such esters of rosin provide adhesive qualities to other finishing agents such as starches, talc, softeners, etc., and when used with such materials very surprisingly produce on textile'fabrics a body and fullness superior to that obtainable without the specific rosin esters regardless of the concentrations of the other materials employed.

In carrying out the method in accordance with this invention, a textile fabric is treated with a dispersion containing as the essential constituent a polyhydric alcohol ester of a rosin, melting within the range of about 35 C. to about 70 C. By the term "dispersion" is meant an organic solvent solution, an aqueous emulsion, an aqueous solution, or an aqueous emulsion formed by dispersing an organic solvent solution of the rosin ester in water. In addition to the rosin ester, the dispersion used in providing the various advantageous features of this invention may contain any of the usual textile finishing materials such as starches, gums, talc, softeners, etc.

More particularly, in carrying out the method in accordance with this invention. a textile fabric is treated with a dilute dispersion containing as I an essential ingredient a polyhydric alcohol ester air, with a hot iron at a temperature within the range of about.160 F. to about 400 F., and preferably within the range of about 200 F. to about 300 F. The exact temperature used for drying will depend on the particular composition containing a polyhydric alcohol ester of rosin which has been used and on the particular cloth dry composition remaining in the fabric will, at

the end of my procedure, be insumcient' fully to impregnate the individual threads or to form a continuous coating over the surfaces of the textile fabric.

The temperature at which the finishing compositions are applied to textile fabrics in accordance with this invention is not critical. The usual procedures used in the industry are entirely satisfactory and the use of the usual drying equipment consisting of dry cans and tenter frames is also satisfactory. I The improved product produced in accordance with this invention comprises a textile fabric which has been treated with a dispersion containing as an essential constituent a polyhydric alcohol ester of a rosin, melting within the range of about 35 C. to about 70 C. The finished textile fabric is characterized broadly as having an improved, flexible finish. Dependingon the type of fabric treated and the auxiliary finishing agents such as starches, gums, talc, softeners, etc., used with the rosin ester, the finished textile fabric will have various other advantageous properties. Thus, a spun rayon treated with a dispersion of the rosin ester alone will possess a very satisfactory handle and body. The back filled fabric produced with use of starch, talc, softeners, etc. as auxiliary agents with the rosin ester in the finishing composition will not be subject to "dusting out" of the starch, will be more fiexible than the usual starch filled fabric and will show improved resistance to breaking of the fabric. If the back-filled fabric is colored, the shade will be cleaner and brighter both on the back and the face than obtainable without the inclusion of the specific rosin ester in the finishing compositions. If the fabric has been dyed after the finishing treatment, a greater depth and brightness of shade is obtainable than with comparable finished fabrics not containing the rosin ester. If the textile fabric has been dyed before the finishing treatment, it will also exhibit increased color brightness. A hosiery fabric treated in accordance with the invention will have improved run-proof properties.

In the preparation of the emulsions for use in the method of this invention, any of the wellknown emulsifying agents may be employed, such starch, for example, for back filling, the starch,

talc and softener mixture is preferably mixed thoroughly with agitation provided by mechanical means or by steam and heated to boiling.' When the mix reaches the boiling point, the emulsion of the polyhydric alcohol ester of rosin is added and the mixture boiled until the starch gelatinizes. On gelatination of the starch, the rosin ester becomes an intimate part-of the starch gel structure, forming a smooth, creamy mixture. The cooking time of the starch mixture is preferably reduced with use of the rosin ester emulsion, about one-half the normal time being satisfactory.

The polyhydric alcohol ester of a rosin may be used in various proportions in the finishing composition depending on the weight of fabric desired, the temperature of application and the particular fabric being treated. The amount of polyhydric alcohol ester of a rosin used with the other finishing agents, such as starches, talc, gums, softeners, etc., will depend entirely on the particular effect desired. With the larger proportions of the rosin ester in such finishes the advantages of the invention will be more pronounced.

The polyhydric alcohol esters of rosin which may be utilized in accomplishing the improvements in textile fabrics described in accordance with this invention are compositions characterized by permanent thermoplasticity and high flexibility. They are essentially water-insoluble and, therefore, remain to a substantial extent in the fabric after laundering.

The rosin used in the production of the rosin esters utilized in this invention may be either wood rosin or gum rosin, such as American or French gum rosin. It may also be hydrogenated forms of such rosins. The acids derived from such rosins, for example, abietic acid, pimaric acid, sapinic acid, etc., may likewise be used equivalently in place of the rosins themselves. With use of hydrogenated rosin, esters of lighter color and having less tendency to discolor on exposure to elevated temperatures may be obtained.

As polylrvdric alcohols for esterifying the rosin to produce the rosin. esters utilizable in the method of this invention any polyhydric alcohol which is capable of esterification with rosin, either alone or in admixture with another polyhydric alcohol, to yield an ester melting within the range of about 25 C. to about C. is contemplated. Thus, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerol, diglycerol, etc., or mixtures thereof may be employed.

The polyhydric alcohol esters of rosin may be prepared by procedures well known in the art. The diethylene glycol ester of rosin may be prepared, for example, by heating together approximately equivalent proportions of rosin and diethylene glycol in accordance with the process of U. S. Patent 1,779,710 to George M. Norman. Preferably,. however, a wood rosin of pale color may be heated with a small excess of diethylene glycol up to a temperature of about 265 C. in about 2 hours, then continuing the heating at a temperature of about 265 to 270 C. for a period of about 4% hours to about 24 hours, depending onthe degree of esterification desired. By heating for about 4 hours at about 265 to 270 C.. a product having an acid number of about 50 will be. obtained, with 8 hours heating the acidity will be reduced to about 2! and with about 18 hours heating a product having an acid number of about 7 will result. 'Before heating is discontinued, any unreacted glycol is removed by reducing the pressure on the vessel to about 15 mm. of mercury for about A hour. An esterification catalyst, such as, for example, boric acid, zinc, etc., may be used to accelerate the esterification. When a catalyst, particularly boric acid, is used it may be desirable to wash the ester with water to remove the catalyst. Washing at a temperature of 90 to 100 C. is effective. By carrying' out the esterification for about 18 hours will have an acid number of about 7, a melting point of 48 to 51 C. and a color of 30 to 40 amber.

In a similar manner, the ethylene glycol ester of rosin may be prepared for use in the method of the invention by heating rosin, either wood or gum, with ethylene glycol. Thus, for example. approximately equivalent proportions of wood rosin and ethylene glycol may be heated gradually over a period of about 3 hours to a temperature of about 250 C. and the heating con tinued at that temperature until the ester has a sufiiciently low acid number. By heating at 250 C. for about hours, for example, the ester will have an acid value of about 33 and a melting point (Hercules drop method) of about 69 C.

The propylene glycol ester of rosin may be prepared in a similar manner or at a slightly higher temperature. Thus. for example, N-wood rosin may be heated with an amount of propylene glycol equivalent to about a 30 per cent excess over the amount theoretically required. By heating at a temperature raised gradually from 220 C. to about 270 C. over a period of about 50 hours, followed by removal of the unreacted glycol under vacuum, an ester having an acid number of about and a melting point of about 65 C. will be obtained.

A diglycerol ester of rosin useful in this invention may be conveniently prepared by heating. for example, i320 parts by weight of N-wood rosin with 166 parts by weight of diglycerol at a temperature of about 265 C. until an ester having a low acidity results. By heating for about 5 hours. for example, an ester having an acid number of about and a melting point of about 90.5 C. may be prepared.

Although the preparation of any of the rosin esters utilized in this invention may be carried out by continuing the esterification to a point which will yield substantially the neutral ester. it is not necessary to do so within the scope of the invention. The esters having an acid number of about 50 contain a considerable percentage of the mono ester, yet they provide the desirable features of the invention. The products of highest utility, however. and these most preferred, are the esters which have a relatively low acid number.

To illustrate the production of the improved textile fabric in accordance with this invention. the following examples are cited:

Example I A solution of a diethylene glycol ester of rosin having'an acid number of 2'7 and a melting point of 50 C. was prepared as follows:

This solution was mixed with parts by weight of sulfcnated tallow 3.5 parts by weight of sodium hydroxide and 1880 parts by weight of water and agitated until a smooth emulsion resuited. A 2.85 oz. cotton cloth was then padded through the emulsion and the excess squeezed out between rubber wringer rolls. The impregnated cloth was then dried over cans at a temperature of about 250' F. As a result of the treatment, the finished cloth had acquired a full, well-bodied. flexible finish without boardiness, these features being retained, to a substan tial extent after laundering.

Example 2 spun rayon was treated with the same emulsion used in Example 1. and in a similar manner. A full, well-bodied finish which resisted wrinkling and which was not materially affected by dry cleaning fluids, particularly of the gasoline type,was produced.

.Ezample 3 An emulsion was prepared from parts by weight of a solution of thediethylene glycol ester of rosin prepared as in Example 1 with 1500 parts by weight of water containing 3 parts by weight of sodium hydroxide. A 7 oz. duck cloth was impregnated with the emulsion and dried as in Example 1. As a result, the cloth acquired a stiff. yet flexible finish without boardiness.

- Example 4 An emulsion was prepared from 50 parts by weight of a solution of the diethylene g ycol ester of rosin prepared as in Example 1, with 1000 parts by weight of a watersolution containi 50 parts by weight of corn starch, 100 parts by weight of tale, 5 parts by weight of sodium hydroxide, and 5 parts by weight of sulfonated tallow (50%) by heating to 160 F. with agitation. A 3.70 oz. cotton fabric of dark brown shade was back filled with the emulsion on a back filling machine. After drying at a'temperature of about 200 F., the cloth was well filled and the starch and talc could not be readily dusted out. The color of the finished cloth closely matched the color of the unfinished sample. The cloth showed no crocking of the dye.

Example 5 An emulsion of a diethylene glycol ester of rosin having an acid number of l and a. melting point of 50 C. was prepared by emulsifying 100 parts by weight of an 80% xylol solution of the ester in parts by weight of water with 0.4 part by weight of Duponol ME and 0.8 part by weight of sulfonated castor oil (75%). The emulsion so prepared contained mil of the rosin ester. A back filling. composition was prepared by heatin'g a mixture of 100 lbs. of corn starch, 200 lbs. of talc and 5 lbs. sulfonated tallow(50%) to a boil and then adding 100 lbs. of the above emulsion of a diethylene glycol ester of rosin and boiling until the starch gelatinized. Water was added to bring the volume up to 88110115- This finishing composition was then used to back fill 80 x 60 broadcloth. applying the mixture to the cloth on a padder. The cloth was then dried over cans at a'temperature of about 220' F. and stretched on a tenter frame. The resultin fabric showed much less dusting out than comparable fabrics finished without the rosin ester emulsion.

Example 6 The emulsion of the diethylene glycol ester of rosin prepared as described in Example was used. Preparation of a backfilling composition was carried out in a. similar manner to the composition described in Example 5' but according to the following formulation:

"Pounds Tapioca star h l5 Com star h 125 Talc 400 Sulion'ated taliow (50%) 50 Sulfonatedteaseed oil. s 16 Converted pot. starch.- 45

Emulsion of diethylene glycol of rosin (Example 5) 100 Water was included to bring the-volume up to 220 gallons. This composition was used to back fill 3.75 yard sheeting. (48 x 44 construction) in white 'and in colors. The resulting fabrics showed no dusting. whereas without the rosin ester emulsion considerable dusiing occurred. Cleaner and brighter shades of the back and the face of the colored fabrics than possible without the rosin ester emulsion resulted.

Example 7' The emulsion of the diethylene glycol ester of rosin prepared as described in Example 5 was .used to prepare a back filling composition according to the formulation:

Pounds Corn star h 120 Sulfonated taliow (25%) 20 Emulsion of diethylene glycol ester of rosin (Example 5) 75 The composition was prepared by heating the starch. talc and sulfonated taliow to a boil, then adding the emulsion of the diethylene glycol ester of rosin and boiling for 3 minutes to gelatinize the starch. The composition was made up to 300 gallons by dilution. This finishing mixture was used to back fill 3.35 yard pocketing cloth dyed to a brown color. The procedure described in Example 5 was followed. The resulting fabric showed no dusting of the starch or talc and the finish showed no breakdown on aging. The color of the back and the face were about the same.

Example 8 Twenty pounds of the emulsion of the diethylene glycol ester of rosin prepared as in Ex ample 5 were added to a mixture containin 10 pounds of corn starch and pounds of sulfonated -teaseed oil which had been brought to a'boil and the boiling continued until the starch gelatinized. The composition was made up to 150 gallons, and applied as a pure finish to 112 x 60 broadcloth. applying the finish in the nip between two rolls with the bottom roll immersed in the composition. The broadcloth was then dried on a tenterirame to the desired width at a temperature of 250-280 F. and then given a light calendering with cold rolls. The resulting broadcloth had a full and well-bodied finish. The fabric showed no dusting out of the finish upon handling.

Example 10. A solution of 132 parts by weight of the dim ethylene glycol ester of rosin in 33 parts by weight of xylene was emulsified to a smooth emulsion by stirring for about 5 minutes with 200 parts by weight of water containing 1.5 parts by weight of sodium lauryl sulfate.

Then 600 parts by weight of the above emulsion were added to 3310 parts by weight of water containing 50 parts by weight of sulfonated taliow (25%). Spun rayon was padded through the diluted emulsion and air dried at 190-210 F. for 3 minutes. then wetout and ironed dry. As a resuit, a full finish having draping qualities was imparted to the rayon. The finished rayon was resistant to wrinkling and to dry cleaning fluids.

Example 11 Using the diluted emulsion prepared in Example 5, 80 x 80 print cloth was padded through the emulsion. The cloth was after-treated with a one per cent solution of sodium perborate. After drying and ironing as in Example 5, a semistifi, full,-fiexible finish resulted.

Example 12 Lace curtain material was padded through a solution of 5 parts by weight of a diethylene glycol ester of rosin and 95 parts by weight of xylene and the impregnated material dried by ironing at 225 F. The finish produced was semistiff and resistant to a substantial extent to laundering.

Example 13 An emulsion was prepared by melting a mixture of 33 parts by weight of a diethylene glycol ester of rosin and 11 parts by weight of paraffin wax and adding with agitation to a boiling mixture of 153 parts by weight of water containing 1.75 parts by weight of triethanolamine and 4.5 parts by weight of stearic acid. A stable emulsion was formed. The emulsion was then diluted with warm water to 3 per cent total solids and a silk stocking treated in the emulsion for 5 minutes at a temperature of 120 F. After drying on a frame for one minute the stocking had acquired a finish which was splashproof and highly resistant to runs.

Example 14 A diethylene glycol ester of hydrogenated N- wood rosin saturated to the extent of about per cent of both double bonds was employed to prepare a finishing composition. The ester had an acid number of 24, a melting point (Hercules drop method) of 42 C. and a color of 12 amber. An emulsion was prepared byadding 140 parts by weight of water containing 0.4 part by weight of Duponol ME and 0.8 part by weight of sulfonated castor oil to 100 parts by weight of an per cent xylol solution of the hydrogenated rosin ester with agitation. The emulsion was homogenized by one pass through a colloid mill. Thirty pounds of the above emulsion containing 33%); solids were diluted to lons with water. This finishing composition was then used to impregnate 6 oz. duck. After removing the excess of the finishing composition cost. This advantage results from the fact that and drying the fabric over cans at a temperature of 220 to 240 F., the finished fabric was full, well-bodied and flexible. It showed unusualresistance to discoloration on ironing and on being subjected to elevated temperatures.

Example 15 The emulsion containing the diethylene glycol ester of hydrogenated rosin prepared as in Example 14 was used to formulate a back filling composition according to the formulation andprocedure described in Example, above. In a similar manner to the procedure of Example 5, the composition was used to back fill 80 -x 20 broadcloth. The resulting fabric showed very little dusting out and on ironing or heating at elevated temperature showed substantially no tendency to discolor.

Example 16' An emulsion was prepared by adding 100 parts' by weight of an ethylene glycol ester of wood rosin having an acid number of 33 and a meltgreater yardage is obtained, for example, from a starch composition containing the specific rosin It will be understood that the details and examples hereinbefore set forth are for purposes of illustration only and that the invention as herein broadly described and claimed is in no way limited thereby.

This application forms a continuation-in-part of my application, Serial No. 223,227, filed Auing point of 69 C. to a boiling mixture of 140 parts by weight of water containing 0.4 part by weight of sodium lauryl sulfate and 0.8 part by weight of 75% sulfonated castor oil. The emulsion was homogenized by passage through a colloid mill at .002 inch setting. A stable emulsion was formed. The emulsion was then diluted withv Example 17 Seventy parts by weight of a diethylene glycol ester of wood rosin having an acid number of 7 and a melting point of 50 C. and parts by weight of a diglycerol ester of wood rosin having an acid number of 15 and a melting point of 90.5 were blended. The hot blended mixture was emulsified by adding to a boiling mixture of 140 parts by weight of water containing .4 P by weight of sodium lauryl sulfate. and .8 part by weight of sulfonated castor oil. The emulsion was homogenized by passage through a colloid mill at .002 inch setting. A treating solution mixture was then prepared by adding 100 parts by weight of the above emulsion, 50 parts by weight of wheat starch, 100 parts by weight of talc, 15 parts by weight of sulfonated teaseed oil to 1328 parts by weight of water. Samples of 8 oz. duck cloth were then impregnated by treatment in the above mixture, excess emulsion removed and the cloth dried over cans at a temperature of about 265 F. The duck cloth as a result of the above treatment had acquired a full, well-bodied finish. Due to the binding action of the rosin ester, the starch particles were not dusted out on shaking of the cloth.

' The many advantages of the treatment of textile fabrics with finishing compositions containing as an essential ingredient a polyhydric alcohol ester of a rosin as described in the above with particular reference to the type of fabric treated and to the effect of the specific rosin ester on the usual finishing materials such as starches, gums, talc, softeners, etc., when used in conjunction with such materials. In addition to these advantages it will be readily apparent that the finishes are easy to apply. A greater general uniformity of finishes is obtainable and at a cost which presents a reduction in finishing gust 5, 1938, entitled "Textile finishing, diethy1- ene glycol ester of rosin."

What I claim and desire to protect by Letters Patent is:

1. Process of finishing a textile fabric which includes treating the fabric with a dispersion containing a glycol ester of a rosin, said ester having a melting point within the range of about 35 to about 70 C.

2. Process of finishing a textile fabric which includes treating the fabric with a dispersion containing a glycol ester of a rosin, said ester having a melting point within the range of about 35 to about 70 C., removing excess dispersion from the fabric and drying the fabric at a suitable elevated temperature.

3. A textile fabric containing as a finishin agent a. glycol ester of a rosin, said ester having a melting point within the range of about 35 to about 70 C.

4. A textile fabric containing as a finishing agent an ester of diethylene glycol and rosin.

5. A textile fabric containing as a finishing agent an ester of ethylene glycol and rosin.

6. Process of finishing a textile fabric which includes treating the fabric with an aqueous emulsion containing a. glycol ester of a rosin, said ester having a melting point within the range of about 35 C. to about 70 C.

7. Process of finishing a textile fabric which includes treating the fabric with a solution containing a. glycol ester of a rosin, said ester having a melting point within the range of about 35 C. to about 70- C.

8. Process of finishing a textile fabric which includes treating the fabric with a dispersion containing starch and a glycol ester of a rosin, said ester having a melting point within the range of about 35 C. to about 70 C., removing excess dispersion from the fabric and drying the fabric at a suitable elevated temperature.

9. Process of finishing a textile fabric which includes treating the fabric with a dispersion containing starch, a softener and a glycol ester of a rosin, said ester having a melting point within the range of about 35 to about 70 C., removing excess dispersion from the fabric and drying the fabric at a suitable elevated temperature.

10. Process of finishing a textile fabric which includes treating the fabric with a dispersion containing an inert filler and a glycol ester of includes treating the fabric with a dispersion containing a softener and a glycol ester of a rosin, said ester having a melting point within the range of about 35 C. to about 70 'C., removing excess dispersion from the fabric and drying the fabric at a suitable elevated temperature.

. 12. A dyed textile fabric containing as a finishing agent a glycol ester of a rosin, said ester having a meiting point within the range of about 35* C. to about '10 C.

13. A spun rayon fabric containing as a finishing agent a glycol ester of a rosin, said ester having a melting point within the range of about 35 C. to about '10 C.

14. A textile fabric containing as a finishing agent a glycol ester of a hydrogenated rosin. said ester having a melting point within the range of about 35 C. to about 70 C.

WYLY M. BILLING.

CERTIFICATE OF comcnon. Patent No. 2,2 11,52. June 50, 191 2.

WYLY 1'1. BILLING.

,It is hereby certified that error appears in'the printed specification of the above numbered patent requiring correction as ifollows: Page 5, first column, line 12, after "esterifiohtion" insert the following:

--in an inert atmosphere for example nitrogen, carbon dioxide etc., the reaction product will be pale in color.

The ester of diethylene glycol and flood rosi-n produced in accordance with the above examples with'about 8 hours heating at 265 to 270 0-, will have an acid number of aboixt 27, a melting point (Hercules drop method) of about 50 C. anda Lovibond color of about 0 amber. The ester resulting from heating at 265 to 270 c.-;

and vline 14.0, beginning with "A diglycerol'K strike out all to and including the word and period "prepared. in line 11.8; and that the said 1 l.etters Patout should be read with this correction therein that the same may conform to the record of the case in the Patent Office.-

.Signed and sealed this 1st day 01 September, A.-D. 19h2.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. 

